Triple ether lubricant



.oxygen ether linkages.

as acrylic resins of the stated molecular weight, solubility, andstability.

This composition has a viscosity of 14.2 centistokes at 100 degrees F.,and 50.2 at 32 degrees F.; no cloud point and a pour point of minus 90degrees F. This formulation of the composition provides compatibilitywith mineral oils and with mineral-type cleaning solvents, that is,aliphatic and alicyclic compounds; hence, it may be employed withoutpreliminary removal of hydrocarbon lubricant oils, and may be introducedto bearing surfaces as a penetrating oil in admixture including amineral-type cleaning solvent having a vapor tension at exposuretemperature sufficiently high to promote the early escape thereof, e.g., a cleaning naphtha or benzine.

Example I Va A composition, with 100 parts by weight of beta, betaprime-diamyldithiodlethyl ether, 0.20 part of tertiary butyl catechol,0.50 part of tri-nbutylamine rosinate, and 4.50 parts of an acrylicresin as above, has essentially the physical properties andcompatibility of Example IV. In general, the dithiomonoxy ethers set outcan be employed in the absence of an additive ester, as the triple etheris the dominant or basic lubricating agent in the formulations while theadditive ester improves the solvent power and the evaporationresistance.

A major ingredient in each of these examples is a linear triple etherhaving two sulfur and one A general formula for such substances is. AS--BO-B'--S-A; in which A and A are saturated aliphatic groups of 2 to 18carbon atoms; S represents the sulfur ether linkage; B and B aresaturated aliphatic groups containing 2 to 18 carbon atoms; andrepresents the central oxygen ether linkage. The total number of carbonatoms in the four alkyl groups, A, A, B, B, should be at least 10, toavoid excess volatility; and less than about 32 when the material musthave a pour point below minus 60 degrees F. The total number of carbonatoms is a dominant factor in determining the viscosity level-it ispreferred to have an odd number of carbon atoms in the intermediategroups, as this is accompanied by a lower melting point than that of thehomolog having the next-lower'but even number of carbon atoms. Mixturesof isomers are preferably employed, and such is the result from thepreferred manner of preparation: in addition homologs can be usefullyintroduced: all with the result of preventing crystallizing or freezing,and hence permitting use down to the ultimate pour point limit. Thespecific examples above employ symmetrical triple ethers in which theintermediate linkages at either side of the central oxygen group, andthe terminal groups, are respectively identical hydrocarbon groups: thatis, A, A are each amyl terminal groups, and B, B are eachethylintermediate groups.

Among the other dithiomonoxy ethers which can be employed aredikeryldithiodiethyl ether: keryl is the name herein given to ahydrocarbon group of the 12-14 carbon atom range derived from keroseneand without specific identification of the individual hydrocarbons or ofthe structural connection of the carbon atoms, and is to be regarded asa mixture of isomers and homologs with the stated carbon range. Thiscompound of itself exhibits a viscosity of 16.6 centistokes at 100degrees F., and 95.5 at 32 degrees F., and has 1 apour point of minus 80degrees F. Thus, the viscosity is higher than that of the correspond- 4ing triple ether of the specific examples above, but the compositions inwhich this is substituted for the triple ethers of the foregoingexamples are useful where the demand for continued flow and lubricatingefiect at the low temperature ranges of minus degrees and minus degreesF. are not present. Further, it may be employed without the bridgingaryl ester, when a resin compatible with the keryl-alkyl tri-ether isemployed, inclusive of alkyl-soluble acrylic resins. This compound maybe regarded as coming under the above general formula, wherein A and Aare aliphatic groups of 12 to 14 carbon atoms.

Correspondingly, the unsymmetrical ether having terminal amyl and kerylgroups and intermediate ethyl groups, which may be denominatedamylthioethyl-kerylthioethyl ether, has a viscosity of 9.1 centistokesat degrees F. and 38.7 at 32 degrees F. and a pour point of minus 100degrees F. This material may likewise be substituted into any of theabove formulations, in cases where employment down to the low pourpoints of minus 80 or minus 90 degrees F. is not demanded or can beemployed without a bridging aryl-type ester when the resin isalkyl-compatible and soluble in the ether directly, and then is usefulessentially down to its own low pour point. Suitable resins are set outabove for mixture with keryl compounds.

Symmetrical diamyldithiodi-isopropyl ether has a boiling range (onecomposition of isomers and probably homologs) of -154 degrees C. at 1mm.; a viscosity of 4.3 centistokes at 100 degrees F. and 13.7 at 32degrees F.; a pour point below minus 90; no corrosion on brass or steel;and a surface tension of about 31.8 dynes/cm. This can be substituted inthe above examples and employed in cases where the higher maximumtemperature viscosity relationship is not objectionable.

It is, however, preferred to avoid hydrocarbon linkages including largerside groups or highlybranched chains, that is, the preferred compoundshave the main chain methylene groups dominant, for the reason that theviscosity temperature factor of compounds with large or multiple sidegroups is higher than with'straightchain linkages; and hence preferenceis given to essentially straight-chain groups, wherewith the.

A and A groups may be methyl, ethyl, propyl, butyl, amyl, and up tostearyl; andthe B, B groups have similar carbon numbers in straightchain, and including isomers having few side selected which have boilingpoints above that of I the triple ethers, and which have desirably lowmelting points, so that they serve to reduce the vapor pressure of themixture, to a point below the vapor pressure of the dithiomonoxy etherofitself. 7 Thus, diamyldithiodiethyl ether itself (mixture of isomers)has a boiling range of -465 degrees C. at 1 mm. pressure; a viscosity of4.4 centistokes at 100 degrees F. and 12.9 at 32 degrees F., a pourpoint of minus 90 degrees and is free-from corrosion on brass or steeland 51" has a surface tension of 33.7 dynes/cm. Correspondingly, thebutyl phenylundecanoate (an isomeric mixture) has a boiling range of170-180 degrees C. at 1 mm.; a viscosity of 10.0 centistokes at 100degrees F. and 51.0 centistokes at 32 degrees F.; a pour point of minus85 degrees F. no corrosion on brass or steel; and a surface tension ofabout 34.9 dynes/cm. Amyl phenylundecanoate (mixture of isomers) has aboiling range of 175-185 degrees C. at 1 mm. 10.8 centistokes at 100degrees F. and 55.1 at 32 degrees F.; a pour point of minus 75 degreesF.; no corrosion on brass or steel; and a surface tension of about.34.5-

dynes/cm.

The aralkyl ester of the examples thus serves to assure maintenance ofthe polystyrene resin in S01ution when a very low range of temperaturemust be met. Presumptively, the molecular similarities of the styreneresins and of the aryl group in the ester, on the one hand; and presenceof the long alkyl groups in the ester and in the triple ether, on theother hand, are efiective to maintain inter-solution. Thus, in ExampleIII above, a cloud point appears at minus 20 degrees F. in the absenceof such an ester: but the material continues useful as a lubricantalthough it should not be employed at lower temperature over a greatlength of time. The ester is capable of maintaining such resins insolution at the low temperatures, and correspondingly it will be notedthat the compositions of Examples I and II exhibit no cloud point downto the pouring limit. On the other hand, the ester itself exhibits anexcessively high viscosity and the pour point was too high, as witnessthe pour points ofminus 80 and minus 90 degrees F. for the aboveexamples compared with a pour point of minus 65 degrees F. for acomposition such as 100 parts by weight of n-amyl phenylundecanoate,0.200 part of dodecylpiperidine stearate, 0.100 part of tertiary butylcatechol, and 0.500 part of polystyrene. This composition has aviscosity of 13.9 centistokes at 100 degrees F and 74.0 centistokes at32 degrees F.; a pour point of minus 65 degrees F.; no corrosion onbrass or steel; a surface tension of about 34.4 dynes/cm.; and anevaporation residue of 90 per cent,

The n-butyl phenylundecanoate and the namyl phenylundecanoate areillustrations of organic esters which include a long-chain alkyl groupand an aryl group which in the two examples are provided by thephenylundecanoic acid. Other acid groups can be employed, for examplewith the number of carbon atoms in the alkyl structures, from to 24, e.g. from octyl phenylacetate to amyl phenylstearate, representing a totalof 16 to 30 carbon atoms inclusive of the nucleus. The acids of lowalkyl-carbon number tend toward excessive volatility, and are preferablyto be employed as the esters of long-chain alcohols: so that the totalnumber of carbon atoms in the alkyl chain of the acid and in the alkylchain of the alcohol and including the aryl group, will be from 16 to30. Furthermore, it is not necessary that the aryl group should be in anacid portion: since for example phenylamyl alcohol ester of decanoic orundecanoic acid may be used.

, The dodecylpiperidine stearate is illustrative of long-chainalkylpiperidine soaps which may be employed; each of which has thepiperidine group connected on the one hand to a saturated alkyl chain orbranched chain of 10 to 18 carbon atoms, and on the other hand to anacid group ill 6. having a saturated alkylchain or branched chain of10to 18 carbon atoms.

The tertiary butyl catechol is illustrative of an antioxidant which issoluble in the mixture.

Other catechols and soluble commercial antioxidants may be substituted.

The polystyrene or acrylic'resin is added as a viscosity improver. Thatis, it operates to modify the viscosity at higher temperatures withoutgreatly changing the behavior at lower temperatures. The polystyreneresins .are employed in compositions having an aryl component, such asthe phenylundecanoic esters of Examples I and II and where admixtureswith mineral oils will not occur; while aliphatic resins such as methylto butyl acrylates and methacrylates are employed in the absence of sucharyl compounds (Example IV-a) or where the lubricant may become mixedwith mineral oils and exposed to low temperatures.

While it is presently preferred to employ an ester having an alkyl chainof at least 8 carbon atoms and an aryl group such as phenyl or naphthyl,it is also permissible to employ complex aliphatic alcohol-aliphaticacid esters, such for example as 5-ethy1nonyl-2 undecanoate. In general,such a full substitution is feasible when aliphatic-type resins are usedsuch as the acrylics.

Mixtures of isomers and'homologs are to be preferred, both in the etherand the ester, as they operate to depress the freezing point without amajor increase of the viscosity and of vapor tension at the highertemperatures of operation.

The triple others may be prepared invarious ways, as for example:

I. PREPARATION OF DIAMYLDITHIODI- ETHYL ETHER 2184 grams of a mixture ofisomeric amyl mercaptans and 1430 grams of dichlorodiethyl ether weredissolved in 4000 cc. of methyl alcohol. This solution was agitated bymeans of a mechanical stirrer and was heated over a steam bath untilrefluxing commenced. Steam heating was then discontinued while there wasslowly added a solution composed of 1700 grams of 50 per cent aqueoussodium hydroxide diluted with 850 grams of methyl alcohol. This additionwas made with constant stirring and was made at a rate just sufficientto allow the heat of reaction to keep the mixture vigorously refluxing.After completion of the addition, steam heating was resumed, and thereaction mixture was stirred and refluxed for six hours. The materialwas then permitted to cool, and the precipitated sodium chloride wasseparated by filtration. The methyl alcohol was removed by distillationover a steam bath, and the residual liquid was permitted to separateinto two layers. The lower aqueous layer was drawn oiT and discarded.The oil layer was then washed once with dilute (5%) hydrochloric acidand rewashed several times with fresh water until the washings werefound to be neutral. When the washed oil was distilled at a pressure of1 millimeter of mercury, there were obtained 2152 grams ofdiamyldithiodiethyl ether with a boiling range of -165 C.

II. PREPARATION OF DIKERYLDI'IHIO- DIETHYL ETHER I 34.6 grams ofmetallic sodium were dissolved in 1 liter of ethanol, and to theresulting solution of sodium ethylate were added 325 grams-of mixedkeryl mercaptans (C1: to C14 range). This mixture was stirred andrefluxed over a steam bath for two hours, after which steam heating wasdiscontinued and 107 grams of dichlorodiethyl ether were added at a ratejust sufficient to permit the heat of reaction to keep the mixturerefluxing. After completion of the addition steam heating was resumedand the material was refluxed for an additional two hours. The mixturewas then cooled, the precipitated salt was separated by filtration, andthe alcohol was removed from the filtrate by evaporation over a steambath. The residual oil was washed with dilute hydrochloric acid andrewashed with successive portions of fresh water until the wash waterswere found to be neutral. When the oil was distilled at a pressure of 1millimeter of mercury, there were obtained 120 grams of prodduct with aboiling range of 235 to 250 C.

III. PREPARATION OF AMYLTHIOETHYL- KERYLTHIOETHYL ETI-IER a Preparationof amylthioethyl-chloroethyl ether 200 grams of sodium hydroxide weredissolved in 1000 cc. of water and to this solution were added 520 gramsof a mixture of isomers of amyl mercaptan. The mixture was agitated bymeans of a mechanical stirrer, and was heated over a steam bath. Afterstirring and refluxing had been maintained for one hour, steam heat: ingwas discontinued and 685 grams of dichlorethyl ether was added at a ratejust suificient to permit the heat of reaction to keep the mixturerefluxing. When the addition had been completed, steam heating wasresumed, and the material was continuously agitated and refluxed forfifteen hours. Then the mixture was cooled, the aqueous layer wasseparated and discarded, and the oil layer was washed once with dilutehydrochloric acid and several times with successive portions of freshwater until the washings were found to be neutral. The washed oil wasdistilled at a pressure of 10 millimeters of mercury, and there wereobtained 732 grams of amylthioethyl-chloroethyl ether with a boilingrange of 120 to 130 C.

5. Preparation amylthioethyl-kerylthioethyl ether 69' grams of metallicsodium were dissolved in one liter of ethanol, and to this solution ofsodium ethylate were added 648 grams of mixed keryl mercaptans (C12 to014 range). This mixture was refluxed over a steam bath and stirredcontinuously for one hour, after which time steam heating wasdiscontinued and '74 grams of amylthio ethyl-chloroethyl ether wereadded at a rate just suflicient to maintain continuous refluxing. Afterthe addition of the ether had been completed, steam heating was resumed,and the mixture was stirred and refluxed for an additional 2 hours. Thenthe material was cooled, the precipitated salt was removed byfiltration, and the ethanol was driven off by evaporation over a steambath. The residual oil was washed once with dilute hydrochloric acid andseveral times with successive portions of fresh water until the washingswere found to be neutral. Then the washed oil was distilled at apressure of 1 millimeter of mercury. There were obtained 641 grams ofamylthioothyl-kerylthioethyl ether.

8 CORROSION TESTS In the above examples, the corrosion test wasperformed by submerging a carefully cleaned and bright instrument brassblock 2.5 x 1 x 1 centimeters in size and having an area of 12 squarecentimeters, in about 10 cubic centimeters of the oil in a glass vessel:the temperature was maintained at 100 degrees C. for 100 hours whilepassing oxygen gas saturated with water vapor at 3 bubbles per second(0.2 cubic feet per hour): at the end of test, the lubricant wasexamined for change of viscosity and appearance, and the surface of thebrass block was examined for pitting or other evidence of corrosion andweighed after removing the oil. The viscosity change was not over 5 percent, and the weight loss of the brass block was not over 1 milligramfor the products accepted as non-corrosive: surface staining withoutessential change of weight occurred in some instances. A second test,for corrosion on steel, is made by half-immersing a high-grade cleanedsteel bearing ball in a 20 cc. beaker containing the lubricant, thebeaker being then kept in a sealed vessel containing water to maintain asaturated atmosphere, at room temperature, for a period of severalmonths: satisfactory lubricants resist this test for 5 or 6 months. Athird test, for corrosion on steel, is conducted by immersing such asteel ball in the lubricant at degrees C. for one hour; then addingdistilled water to displace the main body of oil and leave the ballimmersed in the water; and then holding the ball so immersed until morethan 10 per cent of the surface is covered with rust: a satisfactory"lubricant must resist for at least 2 days. (By comparison, mostuninhibited mineral oils of highly refined types fail in a few hoursunder this test: some develop rust spots in a few minutes.)

The evaporation residue is calculated as the percentage of a 1.0000 gramsample of lubricant remaining after passing nitrogen gas at the rate ofone-half cubic foot per hour through the oil for a period of 100 hours,the oil sample being contained in a special cell designed to promotesaturation of the nitrogen with oil vapor, and the entire apparatusbeing maintained at C.

The lubricant use of ethers with triple linkages of sulfur or seleniumis set out and claimed'in the copending Barker and Alter application,Serial No. 552,814, filed September 5, 1944, now Patent No. 2,592,510,patented May 15, 1951. The employment of alkyl piperidine salts is setout and claimed in my copending application, Serial No. 547,979, filedAugust 3, 1944, now Patent No. 2,412,956, patented December 24, 1946.

It is preferred to include small percentages (not exceedingsubstantially l per cent in all) of modifying agent to improve theoiliness and reduce the coefficient of friction to inhibit oxidation ofthe lubricant and of contacted surfaces, to improvetemperature/viscosity relationships, etc.; but care must be taken toavoid the presence during the service of the lubricant of such an amountof mineral oil lubricant as to modify the behavior of the mixture or initself to perform lubricating service unless specific precaution hasbeen taken as in Example IV: this content for Examples I to III, forexample, must never exceed 5 per cent because at this proportion thereprecipitates a dense white cloud at low temperatures. It should be keptas low as possible, and hence thesecompositions can be described asessentially free of mineral oil.

It is obvious that the invention is not limited to the forms of practicedescribed, but that the same Iclaimz.

1. A lubricant having as the dominant and major ingredient thereof mixedpartially isomeric triple ethers of the general formula A-SB-OB'S-Awhere A, B, A and B are saturated aliphatic groups each containing 2 to18 carbon atoms, S represents a sulfur ether linkage, and. represents anoxygen ether linkage; the total number of carbon atoms being from toabout 32, a resin selected from the group consisting of polystyrene andacrylic resins having a molecular weight of 20,000 to 100,000; and,also, including an aralkyl ester ingredient intersoluble with said etherand a solvent of said resin, said ester ingredient being a mixture ofisomers each having alkyl structures of 10 to 24 carbon atoms, theamount of said ester ingredient being less than the amount of etheringredient and characterized in having a pour point not higher thanminus 80 degrees F. and a cloud point not higher than degrees F., theamount of resin being 1 to 4% parts per 100 parts of the ether and esteringredients combined.

2. A lubricant having as the dominant and major ingredient thereof mixedpartially isomeric triple ethers of the general formula A-S-B--OB'-SAwhere A, B, A and B are saturated aliphatic groups each containing 2 to18 carbon atoms, S represents a sulfur ether linkage, and 0 representsan oxygen ether linkage; the total number of carbon atom being from 10to about 32, a resin selected from the group consisting of polystyreneand acrylic resins having a molecular weight of 20,000 to 100,000; and,also, including an aralkyl ester ingredient intersoluble with said etherand a solvent of said resin, said ester ingredient being a mixture ofisomers each having an acid portion formed of an alkyl group of 10 to 24carbon atoms and an aryl group and each having an alkyl alcohol portionof 4 to about 11 carbon atoms, the amount of the ester ingredient beingless than the amount of the ether ingredient; and characterized inhaving a cloud point not higher than minus 20 degrees F., the amount ofresin being 1 /2 to 4 parts per 100 parts of the ether and esteringredients combined.

1 3. A lubricant consisting of 60 parts by weight of beta, betaprime-diamyldithiodiethyl ether, 40 parts of the phenylundecanoic esterof an alkyl alcohol of 4 to 6 carbon atoms, about 0.2

part of an alkylpiperidine soap having alkyl and acid group chains eachof from 10 to 18 carbon atoms, 0.10 part of tertiary butyl catechol, andabout 1.5 parts of a resin selected from the group consisting ofpolystyrene and acrylic resins having molecular weights rangin from20,000 to 100,000.

4. A lubricant consisting of 60 parts by weight of beta, betaprime-diamyldithiodiethyl ether, 40 parts of n-butyl phenylundecanoate,about 0.20 part of an alkylpiperidine soap having alkyl and acid groupchains each of from 10 to 18 carbon atoms, 0.10 part of tertiary butyloateohol, and about 1.5 parts of a resin selected from the groupconsisting of polystyrene and acrylic resins having molecular weightsranging between 20,000 and 100,000.

5. A lubricant consisting of 60 parts by weight of beta, beta primediamyldithiodi isopropyl ether, 40 parts of the phenylundecanoic esterof an alkyl alcohol of 4 to 6 carbon atoms, about 0.20 part of analkylpiperidine soap having alkyl and acid group chains each of from 10to 18 carbon atoms, 0.10 part of tertiary butyl catechol, and about 1.5parts of a resin selected from the group consisting of polystyrene andacrylic resins having molecular weights ranging between 20,000 and100,000.

6. A lubricant having as the dominant and major ingredient thereof about60 parts mixed partially isomeric triple ethers of the general fromulaA-SBOB'S-A' where A, B, A and B are saturated aliphatic groups eachcontaining 2 to 18 carbon atoms, S represents a sulfur ether linkage,and 0 represents an oxygen ether linkage; the total number of carbonatoms being from 10 to about 32; with about 40 parts of an aralkyl esteringredient intersoluble with said ether, said ester ingredient being amixture of isomers each having alkyl structures of 10 to 24 carbon atomsand having a boiling point above that of the said ether ingredient andbeing a solvent for polystyrene in the molecular weight range belowabout 100,000; and about 1 /2 parts per hundred parts of the ether andester ingredients combined of soluble polystyrene resin of a molecularweight between 50,000 and 100,000.

'7. A lubricant consisting of about 60 parts of mixed isomeric tripleethers of the general formula A-SB-O-BS-A, where A and A are saturatedaliphatic groups, and Where B and B are saturated aliphatic groupscontaining 2 to 3 carbon atoms, the total number of carbon atoms formingthe molecular chain with intervening sulfur and oxygen atoms being from10 to 32, and where S represents a sulfur ether linkage and 0 representsan oxygen ether linkage; about 40 parts of an aralkyl ester ingredientintersoluble with said ether and having a higher boiling point than thesaid ether, said ester ingredient being a mixture of isomer each havingalkyl structures of 10 to 24 carbon atoms; together with 0.20 part of analkylpiperidine soap having alkyl and acid chains each of from 10 to 18carbon atoms, 0.10 part of tertiary butyl catechol and 1.5 to 4.5 partsof a resin selected from the group consisting of polystyrene and acrylicresins having molecular Weights ranging between 20,000 and 100,000.

8. A lubricant as in claim 3, and having dissolved therein 2 parts of arust inhibitor selected from the group consisting of salts and esters ofoxidized-petroleum acids, tri-n-butylamine rosinate, di-n-butylaminerosinate, and amylthiopropylipiperidine rosinate.

9. A lubricant having as the dominant and major ingredient thereof mixedpartially isomeric triple ethers of the general formula AS-B-OB--SAwhere A, B, A and B are saturated aliphatic groups each containing 2 to18 carbon atoms, S represents a sulfur ether linkage, and 0 representsan oxygen ether linkage; the total number of carbon atoms being from 10to about 32; and also including about 0.50 part of tertiary butylcatechol; and characterized in having a cloud point not higher thanminus 20 degrees F.

10. A lubricant as in claim 9, in which at least one of the saturatedaliphatic groups is provided by the keryl hydrocarbon group having 12 to14 carbon atoms and the said ethers are present as a mixture of isomersand homologs each responding to said general formula; and characterizedby a pour point of not higher than minus F. and a cloud point not higherthan minus 20 F.

'11 11. A lubricant having as the dominant and major ingredient thereofa mixture of diamylthiodi-isopropyl ether isomers; and characterized bya pour point ofa-not higher than minus 80 F. and a cloud point 'nothigher than minus 5 20 F.

GEORGE E. BARKER.

REFERENCES CITED The following references are of record in the file ofthis patent:

Number 12 UNITED STATES PATENTS Name Date Moran Nov. 12, 1940 Moran Aug.10, 1943 Barker Aug. 15, 1944 Morgan Mar. 5, 1946 Fenske et a1 Sept. 17,1946 Evans Nov. 9, 1946

1. A LUBRICANT HAVING AS THE DOMINANT AND MAJOR INGREDIENT THEREOF MIXEDPARTIALLY ISOMERIC TRIPLE ETHERS OF THE GENERAL FORMULAA-S-B-O-B''-S-A'' WHERE A, B, A'' AND B'' ARE SATURATED ALIPHATIC GROUPSEACH CONTAINING 2 TO 18 CARBON ATOMS, S REPRESENTS A SULFUR ETHERLINKAGE, AND O REPRESENTS A SULFUR ETHER LINKAGE; THE TOTAL NUMBER OFCARBON ATOMS BEING FROM 10 TO ABOUT 32, A RESIN SELECTED FROM THE GROUPCONSISTING OF POLYSTYRENE AND ACRYLIC RESINS HAVING A MOLECULAR WEIGHTOF 20,000 TO 100,000; AND, ALSO, INCLUDING AN ARALKYL ESTER INGREDIENTINTERSOLUBLE WITH SAID ETHER AND A SOLVENT OF SAID RESIN, SAID ESTERINGREDIENT BEING A MIXTURE OF ISOMERS EACH HAVING ALKYL STRUCTURES OF 10TO 24 CARBON ATOMS, THE AMOUNT OF SAID ESTER INGREDIENT BEING LESS THANTHE AMOUNT OF ETHER INGREDIENT AND CHARACTERIZED IN HAVING A POUR POINTNOT HIGHER THAN MINUS 80 DEGREES F. AND A CLOUD POINT NOT HIGHER THAN 20DEGREES F., THE AMOUNT OF RESIN BEING 1 1/2 TO 4 1/2 PARTS PER 100 PARTSOF THE ETHER AND ESTER INGREDIENTS COMBINED.